Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2015 Electronic Supplementary Information for New Journal of Chemistry Polyurethane nanomicelles: Novel eco-friendly and efficient polymeric ionic solvent for Cannizzaro reaction Hamed Daemi, Mehdi Barikani,* Mehdi Jahani Contents Page 1. Experimental section S2 1.1. Materials S2 1.2. General procedure for synthesis of anionic polyurethane nanomicelles S2 1.3. General recipe for Cannizzaro reaction of aromatic aldehydes S2 1.4. Measurements S2 Important characteristic FTIR absorptions of the synthesized anionic polyurethane Chemical characterization of benzoic acid (2b) Chemical characterization of 2-chlorobenzoic acid (3b) Chemical characterization of 4-methoxybenzoic acid (8b) Chemical characterization of 4-nitrobenzoic acid (10b) Chemical characterization of benzyl alcohol (1c) S4 S5 S8 S10 S12 S14 S1
1. Experimental section 1.1. Materials Polytetramethylene ether glycol (PTMEG) with a molecular weight 950-1000 was obtained from Arak Petrochemical Company (Iran) and dried at 50 C under vacuum for 24 h before use to ensure the removal of all impurities and water vapors that may interfere with the reactions of isocyanate functional groups. Dimethylolpropionic acid (DMPA), N-methylpyrrolidone (NMP), isophoronediisocyanate (IPDI), 1,4-butanediol (1,4-BD) and triethylamine (TEA) were purchased from Merck, Germany. All other chemicals were obtained from Aldrich and Merck companies and used without further purification. 1.2. General procedure for synthesis of anionic polyurethane nanomicelles The APUD was synthesized by using a simple prepolymer mixing process. As a summary, both PTMEG and IPDI were placed into the reaction vessel and the temperature of the reactor was increased to 90 C. After the formation of NCO-terminated prepolymer, a solution of DMPA in NMP and 1,4- butanediol were added into the reactor, respectively. After that, an equivalent of TEA was added into the polymer mixture to neutralize the acid functional groups. Finally, a polyurethane dispersion with a 30 wt% solid content was prepared by addition the required amount of deionized water into the reactor at room temperature 1.3. General recipe for Cannizzaro reaction of aromatic aldehydes The conversion of benzaldehyde to benzyl alcohol and benzylic acid (entry 1, Table 1) is described as an example: A mixture of benzaldehyde (1a, 1 mmol) and sodium hydroxide solution (40 mg of 20% w/w, 0.15 mmol) were stirred in the presence of 1 ml of APUD (30% w/w, 0.03 mmol) at room temperature for 3 h. Progress of the reaction was monitored by TLC analysis to observe no aldehyde in the mixture. The product and uncreated materials were separated from APUD by using the n-hexane as a convenient nonsolvent (2 2 ml). The polymeric solvent was used for further reactions after washing. After that, the mixture was neutralized with cold HCl solution (2 M), and the precipitate, aryl acid, was obtained by filtration (1b). Then, the filtrate was extracted and dried with ethyl acetate and MgSO 4 to obtain the aryl alcohol (1c). The melting points, FTIR and NMR spectrometric data of isolated products were compared with the literature and/or authentic samples. 1.4. Measurements The synthesized APUD and the products of Cannizzaro reaction were characterized using the FTIR spectra from a Bruker-Equinox 55 IR spectrometer (Ettlingen, Germany). Melting points were determined using an Electrothermal apparatus. The silica gel 60 F-254 Al-plates (Merck) were used for analytical TLC. The 1 H NMR spectra were recorded in (CDCl 3 ) solution using a Bruker DPX-250 Spectrometer (250 MHz). A Polymer Lab TGA-1500 instrument (London) was served for evaluation of S2
thermal stability of the APUD films under a nitrogen atmosphere with a heating rate of 10 C/min. Stress strain measurements of APUDs were carried out on an Instron Mechanical Testing instrument tensile tester. Young s modulus, also known as the tensile modulus, was evaluated using a tensile tester model 10/M (MTS System Corporation, Eden Prairie, MN) at a strain rate of 50 mm/min. Scanning electronic microscopy (SEM) (Model Vega, Tescan Co., Czech Republic) was used to probe the morphological aspects of polyurethane surface. The morphology of the APU nanomicelles was observed on a transmission electron microscope (JEOL 1200EX). The PU dispersions were diluted to about 0.05 wt % with distilled water. Some drops of the diluted dispersion were inserted on the coated side of a 200- mesh nickel and analyzed after drying. S3
Table S1. Important characteristic FTIR absorptions of the synthesized anionic polyurethane. Bond (NH) NCO (CH) sym str (C=O) urethane (NH) Amide II (CH) asym str (OCO) asym Vibration (cm -1 ) 3319 2945 2859 2795 1714 1538 1463 1365 1305 1111 S4
Chemical characterization of benzoic acid (2b) M.P. 120 121 C, yield: 91%, 1 H NMR (250 MHz, CDCl 3 ) δ (ppm): d 8.12 (dd, J = 7.5 Hz, 2H), 7.62 (t, J= 7.5 Hz, 2H), 7.48 (t, J= 7.5 Hz, 1H). CO 2 H Fig. S1. 1 H NMR spectrum of benzoic acid. S5
Fig. S2. Expanded 1 H NMR spectrum of benzoic acid. S6
Fig. S3. Expanded 1 H NMR spectrum of benzoic acid. S7
Chemical characterization of 2-chlorobenzoic acid (3b) M.P. 139 140 C, yield: 90%, 1 H NMR (250 MHz, CDCl 3 ): δ (ppm): 7.32 7.38 (m, 1H), 7.44 7.50 (m, 2H), 8.02 (d, J = 8 Hz, 1H). CO 2 H Cl Fig. S4. 1 H NMR spectrum of 2-chlorobenzoic acid. S8
Fig. S5. Expanded 1 H NMR spectrum of 2-chlorobenzoic acid. S9
Chemical characterization of 4-methoxybenzoic acid (8b) M.P. 144 145 C, yield: 91%, 1 H NMR (250 MHz, CDCl 3 ): δ (ppm): 7.96 (d, J =7.0 Hz, 2H), 6.86 (d, J =7.0 Hz, 2H), 3.81 (s, 3H). CO 2 H OMe Fig. S6. 1 H NMR spectrum of 4-methoxybenzoic acid. S10
Fig. S7. Expanded 1 H NMR spectrum of 4-methoxybenzoic acid. S11
Chemical characterization of 4-nitrobenzoic acid (10b) M.P. 238 240 C, yield: 90%, 1 H NMR (250 MHz, CDCl 3 ): δ (ppm): 8.11-8.21 (4H). CO 2 H NO 2 Fig. S8. 1 H NMR spectrum of 4-nitrobenzoic acid. S12
Fig. S9. Expanded 1 H NMR spectrum of 4-nitrobenzoic acid. S13
Chemical characterization of benzyl alcohol (1c) Yield: 88%, 1 H NMR (250 MHz, CDCl 3 ): δ (ppm): 3.16 (s, 1H), 4.53 (s, 2H), 7.23-7.33 (m, 5H). CH 2 OH Fig. S10. 1 H NMR spectrum of benzyl alcohol. S14
Fig. S11. Expanded 1 H NMR spectrum of benzyl alcohol. S15